JTTEE5 20:817–828

DOI: 10.1007/s11666-011-9632-2
1059-9630/$19.00  ASM International

Peer Reviewed
Column Formation in Suspension
Plasma-Sprayed Coatings and Resultant
Thermal Properties
Kent VanEvery, Matthew J.M. Krane, Rodney W. Trice, Hsin Wang, Wallace Porter, Matthew Besser,
Daniel Sordelet, Jan Ilavsky, and Jonathan Almer

(Submitted November 15, 2010; in revised form February 15, 2011)

The suspension plasma spray (SPS) process was used to produce coatings from yttria-stabilized zirconia
(YSZ) powders with median diameters of 15 lm and 80 nm. The powder-ethanol suspensions made with
15-lm diameter YSZ particles formed coatings with microstructures typical of the air plasma spray
(APS) process, while suspensions made with 80-nm diameter YSZ powder yielded a coarse columnar
microstructure not observed in APS coatings. To explain the formation mechanisms of these different
microstructures, a hypothesis is presented which relates the dependence of YSZ droplet flight paths on
droplet diameter to variations in deposition behavior. The thermal conductivity (kth) of columnar SPS
coatings was measured as a function of temperature in the as-sprayed condition and after a 50 h, 1200 °C
heat treatment. Coatings produced from suspensions containing 80 nm YSZ particles at powder con-
centrations of 2, 8, and 11 wt.% exhibited significantly different kth values. These differences are con-
nected to microstructural variations between the SPS coatings produced by the three suspension
formulations. Heat treatment increased the kth of the coatings generated from suspensions containing 2
and 11 wt.% of 80 nm YSZ powder, but this kth increase was less than has been observed in APS
coatings.

Keywords APS coatings, PS microstructures, suspension
plasma spray, thermal properties
1. Introduction
Yttria-stabilized zirconia (YSZ) coatings are widely
used in gas turbines to insulate metallic components from
the heat generated during engine operation (Ref 1). These
thermal barrier coatings (TBCs) are commonly applied
through either the electron beam physical vapor deposi-
tion (EB-PVD) or air plasma spray (APS) processes
(Ref 1, 2). In the case of EB-PVD, electron beam heating
of a YSZ ingot produces a vapor that subsequently con-
denses on the substrate (Ref 1, 2). In APS, YSZ powder is
injected into a DC plasma which melts the powder parti-
cles while propelling them onto the substrate (Ref 1-3).
The differences in the two processes lead to distinct
coating microstructures (Ref 4-7).
Kent VanEvery, Progressive Surface, Grand Rapids, MI;
Matthew J.M. Krane and Rodney W. Trice, School of Materials
Engineering, Purdue University, West Lafayette, IN; Hsin Wang
and Wallace Porter, Oak Ridge National Laboratory, Oak
Ridge, TN; Matthew Besser, Ames Laboratory, Ames, IA;
Daniel Sordelet, Caterpillar, Peoria, IL; and Jan Ilavsky and
Jonathan Almer, Argonne National Laboratory, Argonne, IL.
Contact e-mail: rtrice@purdue.edu.
An EB-PVD YSZ coating consists of a collection of
columnar, quasi-single crystals (Ref 6, 7). Typical depo-
sition conditions result in these crystals growing primarily
normal to the substrate surface, which is located directly
above the flux emitted by the vaporized feedstock (Ref 8,
9). The resulting columnar grains, which tend to extend
from the substrate to the coating top surface, usually have
diameters on the order of 10 lm (Ref 6, 7). These grains
contain closed and open pores and are separated from
neighboring columns by a continuous gap that varies in
width from a few nanometers at the substrate to ~1 lm
near the coating top surface (Ref 6, 7).
An APS coating is deposited by liquid droplets that
impact a substrate, spread across the surface, and solidify
into disc-like structures referred to as lamellae (Ref 3, 4,
10). During droplet spreading the liquid may not com-
pletely wet the underlying surface, which will result in
interlamellar pores (Ref 3, 4). Despite the presence of
these interlamellar pores, heat is transferred out of a
spread droplet mainly through the boundary in contact
with the substrate or previously deposited coating (Ref 4,
11, 12). Consequently, as a lamella solidifies, columnar
grains grow perpendicular to this boundary (Ref 10-12).
The contraction accompanying lamella solidification and
cooling generates strains that can form cracks (Ref 4, 11,
12). Since the bonding within grains is stronger than be-
tween them, these intralamellar cracks tend to propagate
along the grain boundaries, cutting the lamella. An APS
YSZ coating is thus composed of lamellae, interlamellar
porosity mainly oriented with radial axes parallel to the
substrate, and intralamellar cracks aligned normal to the

Journal of Thermal Spray Technology Volume 20(4) June 2011—817

 substrate (Ref 4, 10, 12). In the literature cited above, the
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APS microstructure is frequently presented as an arche-
type describing all coatings produced by using a plasma to
melt and deposit YSZ powder; however, as will be pre-
sented here, such a description may not apply to the
coatings resulting from plasma spraying YSZ powders
with single digit micron and smaller diameters.
In APS, the feedstock particles are introduced into the
plasma by a carrier gas (Ref 3). As the particle diameters
decrease, the carrier gas flow rate must increase in order
to inject the less massive particles into the plasma plume
(Ref 3). For most powder materials, the injection of par-
ticles with diameters <5 lm requires carrier gas velocities
that significantly perturb the plasma flow, reducing the
overall deposition efficiency (Ref 3). In addition, the
electrostatic surface forces between micron-sized and
smaller particles can dominate the gravitational body
forces acting on the particles, resulting in particle
agglomeration and an inability to feed material through
the powder supply line (Ref 13). In many cases, the
technical issues associated with spraying micron and sub-
micron diameter powders (i.e., increased carrier gas flow
and feedstock agglomeration) can be solved by spraying
suspensions (Ref 13, 14). Compared to a gas carrier, the
more massive liquid carrier can generate the momentum
required to inject these small powders into the plasma
stream at velocities that do not negatively impact the
coating process. Furthermore, a liquid carrier can contain
dispersants that inhibit powder agglomeration (Ref 3, 13,
15). These advantages have led to the development of the
suspension plasma spray (SPS) technique (Ref 13, 14, 16-
19).
In SPS, the suspension is typically injected into the
plasma plume through a nozzle that produces a coherent
suspension stream or a stream of suspension droplets (Ref
17, 19). Aerodynamic drag forces from the plasma flow
cause the initial stream or droplets to fragment into
smaller, stable droplet sizes (Ref 15, 17). The droplet size
is decreased further as the solvent evaporates (Ref 13, 15,
17). To reduce the enthalpy required for vaporization, a
volatile liquid like ethanol is commonly used for the sus-
pension solvent (Ref 13, 15). Under optimal deposition
conditions, the solvent in the droplet fully evaporates,
leaving individual powder particles or agglomerates that
melt prior to impacting on the substrate (Ref 13, 20).
Achieving these conditions with the micron and submi-
cron droplets generated in SPS requires the use of shorter
standoff distances between the plasma torch exit and the
substrate than is typical for APS (Ref 20). This reduction
is necessary to decrease the occurrence of droplet solidi-
fication prior to deposition. A shorter standoff distance
results in the substrate experiencing a greater heat flux. As
a result, SPS usually involves more substrate cooling than
is used in APS to prevent thermal stress generation within
a coating from causing spallation (Ref 13).
The microstructure of plasma-sprayed coatings can
change as the feedstock powder size is reduced. For
example, decreasing the average powder diameter can
increase the velocity of depositing droplets, which yields
thinner lamellae (Ref 12). Thus, with the ability to spray
818—Volume 20(4) June 2011
submicron feedstocks, the SPS process has the potential to
generate coatings in which the density of interlamellar
pores is significantly larger than what is common in APS
coatings. Such a change is likely to affect the coating
thermal conductivity. At 1250 C, which is close to the
maximum gas temperature at the inlet of a commercial
aircraft turbine engine, photon transport comprises 10%
of the total heat flux through a 6-8 wt.% YSZ ceramic
(Ref 21, 22). Therefore, the majority of the heat transfer
through the YSZ TBCs in aircraft engines occurs by
phonon transport in the ceramic lattice. Increasing the
density of interlamellar pores should cause these phonons
to follow more tortuous paths through the microstructure,
which would lower the coating thermal conductivity (Ref
23). Consequently, SPS could provide a means of
improving the insulating performance of TBCs relative to
current APS thermal barriers. The current study was
undertaken to evaluate this possibility by characterizing
the microstructure and thermal conductivity of YSZ
coatings produced from nanoscale powder feedstock.
2. Experimental Procedures
2.1 Coating Production
SPS was employed to generate coatings from suspen-
sions of two different sized YSZ powders in ethanol. The
particle size distributions within all of the suspensions
employed in this study were measured with a Beckman
Coulter (Fullerton, CA) LS 230 particle size analyzer
(Ref 24). A density of 6.0 g/cm3 and complex refractive
index of 2.16-0.01i were used for powder size calculations
(Ref 24-27).
Micron feedstock suspensions were produced with a
ZrO2-7 wt.% Y2O3 fused and crushed powder from H.C.
Starck, Inc (Euclid, OH) as described in Table 1. No ball
milling was performed on this type of suspension. The
coatings produced from the 15-lm diameter YSZ sus-
pensions will subsequently be referred to as 8 M coatings,
where the number represents the powder loading in wt.%
and the letter represents the powder size, in this case,
micron-sized powders.
The nanofeedstock suspensions contained ZrO2-
8 wt.% Y2O3 powder synthesized by Inframat Advanced
Materials (Manchester, CT). Nanoparticle suspensions
were formulated as detailed in Table 1; the resulting
Table 1 Suspension formulation details
Powder
Suspension conc., wt.% Solventa YSZ particulate d50
8M 8 Ethanol 15 ± 6 lm (volume-based)
2N 2 Ethanol 85 ± 13 nm (number-based)
8N 8 Ethanol 85 ± 13 nm (number-based)
11 N 11 Ethanol 89 ± 13 nm (number-based)
a
Contained 1 wt.% phosphate ester dispersant (Triton QS-44 from
Sigma-Aldrich; St. Louis, MO)
Journal of Thermal Spray Technology
coatings will be referred to here as 2, 8, and 11 N coatings,
respectively, where ‘‘N’’ stands for nanoparticle. After
formulation the suspensions were milled for 3 h on a
rolling jar mill; the grinding media employed for this
process were 9.5-mm diameter by 9.5 mm-long cylinders
of dense YSZ. Following milling no statistical difference
existed between the number-based d50 particle size for 2,
8, and 11 N suspensions.
Coatings were fabricated at Ames Laboratory (Ames,
IA) by spraying directly on 24-grit alumina-blasted copper
substrates that were 2.5-cm wide 9 10-cm long 9 0.5-cm
thick. Suspensions were agitated prior to and during the
spray process using a combination of manual mixing,
ultrasonics, and a magnetically driven stir bar. Further-
more, all suspensions were filtered through a 90 lm sieve,
while being added to the pressure vessel used to supply the
suspension to the plasma torch.
The experimental conditions briefly reviewed below
were determined from a parametric study of the SPS
process employed for this work and were found to mini-
mize the volume fraction of unmelted YSZ powder
observed within the coatings (Ref 28, 29). The plasma
torch was a Praxair (Indianapolis, IN) SG-100 configured
with a 3083-129 cathode, 3083-175 anode, 3083-113 gas
injector, and a 6-mm diameter nozzle. The torch was
operated at a current of 1000 A with primary and sec-
ondary plasma forming gas flows of 20 slpm Ar and
60 slpm He, respectively, which produced a gun voltage of
50 V. The spray direction describing the plasma flow
exiting the gun was perpendicular to the grit-blasted sur-
face. During deposition, the torch rastered horizontally at
29 cm/s across this substrate surface; consecutive passes
were separated by 3 mm. The backside of the substrate
was cooled using air jets with a combined volumetric flow
rate of roughly 2700 lpm. A steel shroud surrounding the
substrate prevented the cooling air from interacting with
the depositing YSZ droplets. The substrate temperature
was not monitored during spraying.
Table 2 lists the spray parameters for the SPS
experiments conducted during this study. All suspen-
sions were injected as coherent streams orthogonal to
the plasma flow. These streams were generated by using
nitrogen gas to force the suspension within a pressure
vessel through plastic tubing connected to a 230-lm
diameter ruby orifice. This orifice was purchased from
Bird Precision (Waltham, MA) and mounted on the
internal injection port of the anode body. The minimum
final coating thickness desired in all experiments was
300 lm.
Table 2 Experimental spray parameters
Suspension 8M 2N 8N 11 N
Standoff, cm 10 5 5 5 iation in directions perpendicular to the beam was plotted
Injection pressure, MPa 29 45 45 45
Suspension flow, mL/min 42 52 52 52
Coating thickness, lm/pass 4 1 6 6
Journal of Thermal Spray Technology
2.2 Thermal Conductivity Measurement
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Thermal diffusivity values were determined for 2, 8,
and 11 N coatings. These measurements were conducted
using the laser flash system located at the High Temper-
ature Materials Laboratory on the Oak Ridge National
Laboratory (Oak Ridge, TN) campus. Test specimens
consisting of 12.7-mm diameter discs were cut into SPS
coatings and removed from the substrate by dissolving the
copper in nitric acid. Before testing, these specimens were
coated with graphite because of the YSZ transparency to
the laser radiation. The test specimens were oriented such
that the effective direction of heat transfer through the
microstructure was parallel to the coating spray direction.
The diffusivity values calculated from the temperature
change were converted to conductivities using YSZ spe-
cific heat data and the bulk density of each sample. Bulk
density and total porosity was measured via an Archime-
des approach. Additional details about this process have
been published previously (Ref 28).
2.3 Small Angle Scattering Experiments
Small angle x-ray scattering (SAXS) experiments were
performed on 2 and 8 N coating samples at the Advanced
Photon Source facility within Argonne National Labora-
tory (Argonne, IL) to characterize the void surfaces within
these microstructures. Because of the high demand for the
beamline needed to generate SAXS data, a second round
of experiments could not be conducted to characterize
8 M and 11 N microstructures. The samples investigated
were obtained by using a robotic diamond saw to cut 1-
mm wide sections along the 12.7-mm diameter of the disc
specimens evaluated in the laser flash diffusivity testing.
Each section was epoxyed to a bolt so that it could be
attached to an electromechanical positioning system and
placed into a 100-lm wide by 30-lm tall beam of colli-
mated, monochromatic x-rays. In these experiments, the
beam was directed onto a coating sample along a path that
was perpendicular to the spray direction. Comparing the
signal strength detected before and after the coating sec-
tion permitted the determination of sample positions that
resulted in the beam passing through the coating section.
By manipulating the sample position, SAXS data were
recorded from a series of adjacent coating volume seg-
ments; for each of the samples tested, the total coating
volume evaluated was roughly 500 9 350 9 1000 lm.
As the x-rays passed through a sample, differences in
the electron densities at the interfaces between the cera-
mic and the gas within cracks and pores coherently scat-
tered waves along small angles from the beam direction
(Ref 30). Some of these waves did not undergo any further
scattering, and, as a result, the associated intensities were
correlated via a Porod constant to the total void specific
surface area (SSA) within the beam interaction volume
(Ref 5, 31). In addition, by recording the scattered inten-
sities with a two-dimensional detector, the void SSA var-
from the intensities of the singly scattered waves. The
direction of each of these scattering events was perpen-
dicular to the void surface (Ref 31, 32). Therefore, the
Volume 20(4) June 2011—819
 data in a given direction on the 2-D intensity plot was the
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result of voids aligned along an orthogonal direction.

For each 2 and 8 N sample, scattering data was col-
lected from only one sample orientation because plasma-
sprayed coatings demonstrate rotational symmetry along a
spray direction perpendicular to the substrate (Ref 31). As
a result, orienting each sample so that the incident beam
was normal to the spray direction yielded results which
could be rotated to form a complete description of scat-
tering from the entire the sample void system (Ref 31).
However, because they were not confirmed by conducting
scattering experiments at multiple sample orientations,
the term apparent is applied to the void SSA results for
the 2 and 8 N samples per the convention of Ilavsky et al.
(Ref 31). A further description of the setup and conditions
for these experiments has been published elsewhere
(Ref 28).

3. Results
3.1 Microstructural Description
Figure 1 shows that the 8 M coating microstructures
were the same as those of a typical APS coating, consisting
of overlapping lamellae that were ~10 lm and larger (i.e.,
longer than the image width) in diameter and several
microns thick. Lamellae often contained multiple intrala-
mellar cracks (Fig. 1a), and interlamellar pores were
observed between lamellae (Fig. 1b). Given the similarity
to APS microstructures, solvent evaporation during the
8 M experiments does not appear to have affected the
coating microstructure morphology.
As shown in Fig. 2, the SPS coatings produced from
nanopowder suspensions were also composed of lamellae.
These lamellae were significantly smaller than those in the
8 M coatings, having single digit micron diameters and
thicknesses in the hundreds of nanometers. Among the
nanopowder feedstock coatings, the lamella diameters
appeared to increase with suspension powder concentra-
tion. For example, the 11 N microstructure in Fig. 2(c)
exhibits lamellae with larger diameters than those shown
in the 8 N microstructure of Fig. 2(a). As the particle size
measurements showed the nanopowder suspensions to
have equivalent d50 values, a difference in lamella size is
likely due to powder concentration differences in the
fragmented suspension droplets within the plume. The
evaporation/combustion of the solvent in these droplets
will eventually cause the powders to touch (Ref 13, 33).
On complete melting, the resulting powder agglomerate
will form one droplet. Agglomerates composed of an in-
creased volume of powders, as would be the case for 11 N
suspensions compared to 8 N suspensions, should lead to
larger droplets. Thus, the suspension powder concentra-
tion in SPS can influence the size of coating microstruc-
tural features in a manner analogous to the powder
feedstock diameter in APS (Ref 34).
Lamellar pores still existed between lamellae in the 2,
8, and 11 N coatings, an example of which can be seen in
Fig. 2(b). However, unlike the 8 M coatings, the majority
Fig. 1 SEM images from an 8 M coating showing (a) a high
magnification of the top surface and (b) a fractured cross section
normal to the substrate
of lamellae visible in micrographs of the 2 N (not shown),
8 N (Fig. 2a), and 11 N (Fig. 2c) top surfaces did not
contain cracks. In fact, intralamellar cracking was only
observed among the largest YSZ lamellae within the 8 and
11 N microstructures. The difference in the contraction
along the lower and upper surfaces during cooling will
increase with the lamella thickness. Consequently, in
comparison to the 8 M lamellae, smaller strains were
generated within the thinner diameter 2, 8, and 11 N
lamellae, which decreased intralamellar cracking in these
microstructures.
As shown in Fig. 3 and 4, the differences between
nanometer and micrometer feedstock fabricated coatings
went beyond lamella dimensions and cracking. Cauli-
flower-like cluster formations comprised the top surfaces
of the 2 N (Fig. 3a), 8 N (Fig. 3b), and 11 N (Fig. 3c)
coatings, although the cluster formations are noticeably
less distinct on the top surface of 11 N coatings than on
those of the 2 or 8 N coatings. Cross-sectional micro-
structures exhibited bands of porosity which resulted in
columnar YSZ structures with diameters of ~100 lm

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Fig. 2 SEM images showing (a) the top surfaces of 8 N lamellae, (b) a lamellar pore between 8 N lamellae, (c) the top surfaces of 11 N
lamellae, and (d) cross sections of fractured 8 N lamellae
(Fig. 4a). In the 2 and 8 N coatings, as shown in Fig. 4(b)
and (c), the columns tended to extend through the coating
thickness. The cross-sectional microstructure of the 11 N
coating was subtly different from those of the 2 and 8 N
coatings in that the 11 N porosity bands tended to merge
(Fig. 4d). This change resulted in fewer columnar struc-
tures spanning the thickness of the 11 N coatings.
3.2 Small Angle Scattering Results
Figure 5 is the SAXS data for an as-sprayed (AS) 8 N
coating. The near circular azimuthal dependence of the
Porod constants calculated from the singly scattered x-ray
intensities is representative of SAXS data obtained for the
AS 2 N coatings previously published (Ref 28), and 2 and
8 N coatings after heat-treatment (not shown) (Ref 28,
29). This result indicates that the combined apparent SSA
of cracks and pores within these coatings was approxi-
mately isotropic. In addition, the SAXS results showed
that the total apparent void SSA decreased by ~30% after
50 h at 1200 C, suggesting sintering occurred during the
heat treatment (Ref 29).
SAXS experiments were not conducted on 8 M coating
samples. However, small angle neutron scattering (SANS)
Journal of Thermal Spray Technology
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investigations (Ref 5, 31, 32) have previously examined
the void SSA orientation in APS YSZ coatings produced
with a spray direction orthogonal to the substrate surface.
The reported findings should be applicable to the 8 M
coatings in the current research. In fact, the work by
Petorak (Ref 32) used the same powder as that employed
to produce the 8 M coatings. The SANS data in these
studies show the APS YSZ coating samples contained
interlamellar pores that were primarily oriented parallel to
the substrate and intralamellar cracks which were mostly
perpendicular to the substrate.
3.3 Thermal Conductivity Results
As an initial evaluation of thermal barrier perfor-
mance, the thermal conductivity (kth) of 2, 8, and 11 N
coating samples were measured. Figure 6 shows temper-
ature-dependent thermal conductivity results from repre-
sentative SPS samples tested in the AS condition, and
after being heat treated (HT) via a box furnace in air for
50 h at 1200 C to simulate TBC service in a gas turbine.
For comparison, corresponding data replotted from Ref 7
and 10 on APS and EB-PVD samples, respectively, is also
included in Fig. 6.
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Fig. 3 SEM images showing the top surfaces on (a) 2 N, (b)
8 N, and (c) 11 N coatings
These data show that, in the AS condition, ranking the
coating types from lowest to highest kth gives APS, 11 N,
EB-PVD, 2 N, and 8 N, with the 11 N and EB-PVD types
being basically equivalent. All heat treatment kth data
exhibited an increase over the corresponding AS values.
The 2 N, 11 N, and EB-PVD values increased by
approximately 0.2 W/m/K, while the APS kth measure-
ments went up on average by 1 W/m/K.
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Fig. 4 (a) Optical cross-sectional micrograph of a 2 N coating
showing columns. Cross-sectional SEM images showing the (b)
columnar structures in a fractured 2 N cross section, (c) porosity
bands in a polished 8 N cross section, and (d) porosity bands in a
polished 11 N cross section
4. Discussion
4.1 Microstructural Development
While the columnar and cauliflower 2, 8, and 11 N
microstructural features are not typical of spray-deposited
coatings, some SPS studies (Ref 14, 20, 35) have reported
these structures. In addition, similar features have been
Journal of Thermal Spray Technology

Fig. 5 A plot showing the azimuthal dependence of the Porod
constants (units of cm 5) calculated from the SAXS of a beam
perpendicular to the spray direction in an as-sprayed 8 N coating.
The Porod shape describes the apparent distribution of the void
specific surface area in a plane perpendicular to the substrate.
The 0/180 axis in the above image is parallel to the substrate
Fig. 6 Thermal conductivity vs. temperature data for as-sprayed
(open points) and heat-treated (filled points) samples from 2, 8,
11 N, APS, and EBPVD coatings. The APS and SPS HT data are
from samples heated for 50 h at 1200 C; EBPVD HT data are
from a sample heated for 100 h at 1100 C. 2 N data are replotted
from Ref 28; APS data are replotted from Ref 10, and EBPVD
data are replotted from Ref 7
observed previously in coatings generated by other spray
or spray-like processes. Kanouff et al. found isolated
columnar deposits on a grit-blasted aluminum plate sub-
strate used in a high velocity oxy-fuel spray experiment for
Journal of Thermal Spray Technology
which the spray direction was ~39 from the substrate
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normal (Ref 36). The columns were separated from where
the spray plume contacted the plate and were attributed to
satellite droplets generated during the impact of the pri-
mary droplets on the substrate (Ref 36). Kanouff et al.
proposed that the spray gases flowing along the plate
surface carried the smaller satellite droplets downstream
of the main deposition region and deposited them on
surface asperities. As the deposition occurred preferen-
tially on the side of the asperity facing the main deposition
region, the deposits grew as columns into the gas flow
transporting the satellite droplets. Hass et al. used the
electron-beam directed vapor deposition (EB-DVD)
process to produce cauliflower-like top surfaces on YSZ
coatings (Ref 8). In these experiments, the angle between
the vapor jet and the substrate surface was oscillated be-
tween 135 and 135, causing most vapor to move along
directions off the substrate normal prior to condensation
(Ref 8). Findings like those published in Ref 8 and 36
suggest that the unique characteristics of the 2, 8, and 11 N
microstructures resulted from the deposition of YSZ
droplets having a significant velocity component parallel
to the substrate.
For a spray deposition process, decreasing the particle,
and hence, the droplet size in the gas/plasma plume in-
creases the sensitivity of these bodies to changes in gas/
plasma velocity. In this study, the plasma flow was direc-
ted normal to the substrate. As a result, near the coating/
substrate the impinging plasma turned and moved across
this surface. This change in the plasma flow exerted drag
forces on the YSZ that tended to slow the droplet velocity
component perpendicular to the substrate and increase
the velocity component parallel to the substrate. Using
numerical modeling, Oberste Berghaus et al. calculated
the effects these forces have on various sizes of zirconia
particles initially traveling at 400 m/s perpendicular to the
substrate and within a plasma flow of equal speed and
direction (Ref 16). These particle velocities are consistent
with droplet velocities measured at 5 cm from the gun face
during SPS experimentation without a substrate (Ref 16).
The results of the model, which have been replotted in
Fig. 7, show that the inertia of a 40-lm diameter zirconia
particle traveling at 400 m/s is large enough to be unaf-
fected by drag from the impinging plasma; however, these
drag forces were determined to affect the trajectories of
400 m/s zirconia particles with diameters between 1 and
5 lm (Ref 16).
Using SEM micrographs like Fig. 2(b) and (d), the
average lamella thickness for all the nanopowder SPS
coatings was measured to be 300 ± 30 nm, where the
interval width captures the central 95% of a t-distribution
describing the lamella thicknesses. The average lamella
diameter in 8 N coatings was estimated from a series of
micrographs like Fig. 2(a). An examination of this repre-
sentative figure shows that the longest dimension visible
for the majority of lamellae is <3.0 lm. Consequently,
3.0 lm was used as the average lamella diameter to esti-
mate conservatively the size of the YSZ droplets depos-
ited while spraying an 8 wt.% nanopowder suspension.
From the above dimensions, the lamellae were formed by
Volume 20(4) June 2011—823
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Fig. 7 Numerical simulation results replotted from Ref 16
showing how the changes in plasma velocity stemming from
substrate impingement and the resulting drag influence the sub-
strate normal velocity component of different diameters of zir-
conia particles within the plasma
YSZ droplets with diameters <2 lm. Therefore, com-
paring the droplet size to the results in Fig. 7 suggests that
drag forces from the impinging plasma caused the flight
paths of all the YSZ droplets in the 8 N experiments to
deviate from the spray direction. Conversely, the plasma
impingement should have produced little change in the
paths of droplets resulting from the 15-lm diameter
powder.
The impact trajectory predictions above led to the idea
that the 2, 8, and 11 N microstructural features, which are
unique from common spray-deposited coatings, result
from directional changes in droplet travel near the sub-
strate. A similar hypothesis was also suggested by other
researchers that found substrate roughness and size
influenced the microstructures of coatings produced dur-
ing SPS with nanosized powders (Ref 35). To develop this
premise further, theories were formulated defining depo-
sition mechanisms leading to the three different micro-
structure types, i.e., those apparent in the 2 N/8 N, 11 N,
and 8 M coatings, observed in this study. For these theo-
ries, the YSZ droplet velocity is 400 m/s perpendicular to
the substrate surface prior to any impingement effects,
and the substrate asperity heights are assumed to be sig-
nificantly larger than the impacting droplet diameters. The
hypothetical deposition mechanisms outlined below may
change for conditions other than those assumed here.
4.1.1 Type 1 Spray Deposition Microstructure Devel-
opment. Microstructures like those of the 2 and 8 N coat-
ings (as revealed in Fig. 3a and b, and Fig. 4a-c) are
proposed to form by a mechanism which will be referred to
as type 1 spray deposition (1SD). In 1SD, YSZ droplets
move with the plasma through the initial turn at substrate
impingement. As a result, the substrate parallel velocity
component of these droplets dominates the substrate nor-
mal component. However, as the plasma flows across the
substrate, the inertia difference between the plasma and
small YSZ droplets cause some of the entrained droplets to
be unable to follow the more sudden directional changes
produced as the plasma moves around surface asperities.
824—Volume 20(4) June 2011
Fig. 8 Schematics illustrating the deposition characteristics
occurring on and away from substrate surface asperities during
(a) 1SD, (b) 2SD, and (c) 3SD. The spray direction is the same in
each figure. The black regions denote the substrate. The light
gray regions represent material deposited by droplets having a
substrate parallel velocity component directed from left to right,
and the dark gray regions represent material deposited by
droplets having a substrate parallel velocity component directed
from right to left
Consequently, 1SD results almost exclusively in droplet
impacts on the sides of surface asperities, as shown in
Fig. 8(a). Initially, deposits formed on substrate asperities
grow both laterally and vertically. During this time, the
lateral growth of taller deposits may engulf shorter depos-
its. Among the remaining deposits of similar heights, the
increase in drag forces generated by the decrease in spacing
separating these structures reduces the plasma flowing be-
tween them. This process eventually causes the lateral
growth to stop, leaving an interdeposit gap. As spraying
proceeds, the ongoing vertical growth of the deposits and
interdeposit gaps produces columnar structures that span
the coating cross section normal to the substrate.
Spraying will naturally yield localized nonuniform dis-
tributions of droplet impacts, which can lead to asperities
in the coating surface. These coating asperities can be-
come sites of preferential 1SD. Consequently, the coating
is expected to have a surface featuring multiple deposits
separated by valleys; these deposits are the cluster for-
mations comprising the cauliflower-like surface structures
mentioned previously.
4.1.2 Type 2 Spray Deposition Microstructure Devel-
opment. Type 2 spray deposition (2SD) is proposed as
describing conditions in which the droplet retains a
velocity directed primarily perpendicular to the substrate,
yet the substrate parallel component still affects deposi-
tion. In this case, the droplets are more massive than those
depositing according to the 1SD mechanism, and they
separate from the plasma before completing the substrate
impingement turn. Consequently, deposition in regions
between surface asperities increases with 2SD. However,
Journal of Thermal Spray Technology
the effects of the impinging plasma drag cause the droplets 4.2 SAXS Analysis with Respect to Deposition

Peer Reviewed
to follow trajectories that result in surface asperities Conditions
shadowing portions of the substrate downstream from the
As shown in Fig. 1(b), an interlamellar pore has an
asperity, which is illustrated in Fig. 8(b). Early in the
orientation similar to the YSZ lamella formed by the
coating process, the shadowing occurring with 2SD will
droplet which created the pore. Therefore, knowledge of
create variations in the growth rate. Figure 8(b) shows the
the orientation of the interlamellar pores obtained from
thickness of the coating deposited in the unshadowed re-
small angle scattering experiments can be used to
gions at the left and right extremes of the figure to be
approximate the lamellae orientations within a coating.
growing twice as fast as that on the substrate asperities.
These experimental results will also include scattering
This difference is because the left substrate asperity blocks
from intralamellar cracks, but, since these cracks tend to
the oblique droplet trajectories from reaching two
run perpendicular to interlamellar pores, the scattering
regions—identified by an absence of light gray bands on
from these two void types will be orthogonal. In addition,
Fig. 8(b)—of the substrate to the right of the peak on this
based on SEM observations, intralamellar cracks are
asperity. Likewise, the right substrate asperity blocks
likely to constitute less of the total void surface area
droplets from reaching two regions—identified by an ab-
than interlamellar pores in nanopowder SPS coatings.
sence of dark gray bands on Fig. 8(b)—of the substrate to
Figure 1(b) shows that plasma-sprayed microstructures
the left of the peak on this asperity. As the height differ-
also contain spherical, intralamellar pores. However, the
ential between the coating in the unshadowed regions and
contribution from this type of pore can be neglected be-
the material deposited on top of the substrate asperities
cause their surface area is small relative to that of intral-
decreases, the deposition on the side of the former will
amellar cracks and interlamellar pores (Ref 5).
increase. This increase causes the unshadowed sections of
The azimuthal dependence of the Porod constants
the coating to grow toward that covering the substrate
calculated using SAXS intensities produced by 2 and 8 N
asperities. Therefore, given a long enough spray time, the
samples were near circular shapes (Fig. 5) (Ref 28).
coating building from the initially unshadowed sections
However, SEM images like Fig. 2(b) confirmed that the
will overgrow that above the substrate asperities. Due to
interlamellar pores in the 2 and 8 N coatings had oblate or
this overgrowth behavior, a coating microstructure formed
lamellar shapes. Therefore, the most probable explanation
by 2SD should exhibit a convergence of the porosity bands
for the isotropy of apparent void SSA in these SPS coat-
separating columnar structures like that observed in the
ings is a near random orientation of the lamellae relative
11 N coatings and shown in Fig. 4(d).
to the substrate plane. Such an orientation is expected for
As with 1SD, the droplet trajectories in the 2SD
coatings generated by 1SD because the droplet impacts in
mechanism promote cluster formations on coating surface
this deposition mechanism result from the plasma flowing
asperities. However, these structures exhibit less growth
around and over surface asperities. Consequently, the
with 2SD than with 1SD because droplets with velocities
planes describing droplet spreading should form a range of
mainly normal to the surface are less likely to deposit
angles with the substrate plane.
preferentially on surface asperities. Therefore, cluster
SANS results correlated to the 8 M coatings suggest
formations will be less distinct on the surface of a micro-
these coatings were composed primarily of lamellae with
structure produced by 2SD than by 1SD.
radial axes approximately parallel to the spray direction.
4.1.3 Type 3 Spray Deposition Microstructure Devel-
Such a microstructure is consistent with 3SD. This mech-
opment. Type 3 spray deposition (3SD) is proposed as
anism tends to generate planar coatings, which increases
describing conditions in which plasma drag forces do not
the probability of an impacting droplet spreading parallel
affect the deposition characteristics, meaning the droplets
to the substrate plane.
yielding 3SD are more massive than those causing 2SD. As
SAXS experiments were not performed on 11 N sam-
a result, 3SD is characterized by deposition on the entire
ples. Based on the earlier deposition theory, the void SSA
substrate surface (Fig. 8c) during each plasma gun pass, i.e.,
orientation in the 11 N coatings could be more anisotropic
droplets do not preferentially impact on surface asperities,
than those of the 2 or 8 N samples, with a greater SSA
and no shadowing occurs from these asperities. The droplet
percentage orientated roughly parallel to the substrate
trajectories required for this complete coverage would be
plane. However, the cauliflower-like surface features and
approximately normal to the substrate surface. Thus, Fig. 7
the kth increase with heat treatment (discussed below)
suggests that 3SD would occur when plasma spraying with
suggest the azimuthal dependence of Porod constants
YSZ droplets having diameters larger than 5 lm.
determined from the SAXS generated by 11 N micro-
The complete substrate coverage possible with 3SD
structures would be nearly isotropic.
prevents the formation of columnar structures separated
by porosity bands (Fig. 8c). In addition, the momentum of
4.3 Thermal Conductivity Discussion with Regard
the droplets in this mechanism should preferentially drive
to 1SD, 2SD, and 3SD Microstructures
liquid into the valleys in the coating/substrate surface.
Thus, coating asperities generated by nonuniform 3SD As the maximum temperature during the laser flash
will not grow into cluster formations; instead, the coating testing was 1200 C, the heat transfer occurred primarily
surface will tend to become more planar than the grit- by phonon transport in the YSZ (Ref 22). Voids within the
blasted substrate surface. This type of deposition produces microstructure inhibit this transport in two ways. First,
the stereotypical APS coating microstructure. because phonons must move around voids, these features

Journal of Thermal Spray Technology Volume 20(4) June 2011—825

 Table 3 Bulk density and total porosity values
Peer Reviewed
for the SPS thermal conductivity test specimens
Coating ID Bulk density, g/cm3 Total porosity, vol.%
2N 3.92 ± 0.06 37
2 N-HT 4.20 ± 0.08 31
8N 5.19 ± 0.06 14
11 N 4.50 ± 0.04 26
11 N-HT 4.56 ± 0.03 25
Each uncertainty interval captures the central 95% of a t-distribution
describing the sample data
increase the average transport distance, and, second, by
constricting the cross-sectional area available for trans-
port, voids increase phonon-phonon scattering interac-
tions (Ref 23). As stated in Section 2.2, the macroscopic
heat flux through the test samples was one-dimensional
and parallel to the coating spray direction. Therefore, both
the amount and distribution of porosity within a micro-
structure affected the sample thermal conductivity
(Ref 37).
A comparison of the density and porosity values in
Table 3 and the discussion of porosity orientation in the
preceding section lead to the conclusion that the kth data
of the 2 N coatings was lower than that of the 8 N coatings
because the former contained more porosity. Conversely,
the 11 N sample contained less porosity than the 2 N
sample, yet the 11 N porosity distribution caused this
specimen to have lower kth values. The 11 N microstruc-
tures were the only ones observed to contain porosity
bands that interconnect, which creates more conduction
pathway restrictions than the linear 2 N/8 N bands. Since
the porosity bands are significantly larger than intrala-
mellar cracks or interlamellar pores, it is not surprising
that the 11 N porosity was more effective at reducing heat
conduction than that of the 2 N specimen.
The increase in coating thermal conductivity data
following heat treatments at 1100 and 1200 C suggest
microstructural void changes occurred during heating. At
these temperatures a YSZ microstructure will undergo
sintering, resulting in crack closure and pore spherodi-
zation (Ref 5, 10, 38, 39). These processes resulted in a
30% decrease in the total apparent void SSA observed
between the AS and heat treated 2 and 8 N SAXS
samples (Ref 29). Similarly, Petorak (Ref 32) reports the
total apparent void SSA in APS YSZ coatings decreased
by 16% after 3 h at 1200 C. Following 100 h at 1100 C,
the SSA of the open and closed porosity in the EB-PVD
YSZ coatings of (Ref 40) each decreased by 68%. Al-
though each coating type exhibited a void SSA reduc-
tion, the corresponding average kth increases do not
correlate linearly with the SSA changes. As shown in
Fig. 6, the kth values for the 2 N and EB-PVD samples
increase an average of 0.2 W/m/K between the AS and
HT measurements, while Ref 32 reports a 0.54 W/m/K
average kth increase after heating APS YSZ samples for
3 h at 1200 C.
The disparity in the sensitivity of coating thermal
conductivity to heat treatment between EB-PVD and
826—Volume 20(4) June 2011
APS YSZ samples can be attributed to the influence of
void structure on this property. In the as-deposited con-
dition, the columnar grains forming an EB-PVD YSZ
coating contain rows of isolated pores which are submi-
± 2 cron in size and separation (Ref 7). Sintering of these
± 2 coatings causes pore spheriodization, during which some
± 1 pores grow at the expense of others (Ref 7). However,
± 1
± 1
even after 100 h at 1100 C, the EB-PVD YSZ void
structure still consists of isolated pores that are submicron
in size and separation (Ref 7). On the other hand, the
intralamellar cracks in an AS APS YSZ coating can link
interlamellar pores to produce void networks (Ref 31,
38). The destruction of these networks via crack closure
during sintering can leave isolated interlamellar pores
separated by millimeter-sized gaps, significantly raising
the coating kth (Ref 32, 38). In fact, the results of Ref 10
and 32 show that roughly half of the kth increase for APS
YSZ coatings after a 3-50 h, 1200 C heat treatment can
be attributed to crack closure. As for the relative kth in-
creases associated with pore spheroidization, APS YSZ
interlamellar porosity tends be oriented more normal to
the spray direction than the intracolumnar porosity is to
the EB-PVD column growth direction (Ref 6, 7, 31, 32,
38). Consequently, when the macroscopic heat flow
direction is parallel to the APS coating spray direction
and the EB-PVD column growth direction, pore spher-
iodization will have a greater effect on the kth of the
former coating type.
The void structure of the nanopowder SPS coatings in
this work was more typical of an EB-PVD YSZ coating
than an APS YSZ coating. The extent of intralamellar
cracking present in micrographs of these SPS coatings
suggests crack-pore void networks were rare, meaning the
interlamellar pores were mainly isolated like intracolum-
nar EB-PVD pores. In addition, the SAXS results indicate
the majority of intralamellar pore SSA to be aligned along
directions that cannot be considered roughly perpendicu-
lar to the spray direction. As a result of the similarities, the
kth increase seen in Fig. 6 between the AS and HT SPS
samples shows a better agreement with the corresponding
change in the EB-PVD data than that for the APS data.
5. Summary
The SPS process was employed to produce coatings
from suspensions containing 15 lm and 80-nm diameter
YSZ powders. Suspensions containing 8 wt.% of 15 lm
powder (8 M) resulted in the well-known spray deposition
microstructure—overlapping lamellae primarily oriented
parallel to the substrate. Conversely, the 80 nm powder
suspensions yielded unique microstructures in which
lamellae formed columnar structures topped with cauli-
flower-like formations. When spraying suspensions con-
taining 2 wt.% (2 N) or 8 wt.% (8 N) nanopowder, the
columns were composed of an approximately random
orientation of lamellae and were separated by linear
porosity bands. With an 11 wt.% (11 N) powder suspen-
sion, interconnected porosity bands were observed.
Journal of Thermal Spray Technology
 Hypotheses on the formation mechanisms producing
these coatings were developed from microstructural
observations and predictions of droplet flight paths. This
information suggests that the change in relative influences
of drag and inertial forces with YSZ droplet size can result
in three types of spray deposition. For 1SD, the plasma
drag forces during substrate impingement dominate the
droplet inertia and redirect the droplet velocity from
normal to along to the substrate surface. Consequently,
droplets impact preferentially on asperities, generating
deposits that grow to become columnar structures sepa-
rated by linear porosity bands. The 1SD microstructure is
analogous to that of the 2 and 8 N coatings from this
study. With 2SD, the droplet velocity remains mostly
normal to the substrate surface, but the impinging plasma
drag influences the droplet trajectories such that surface
asperities block deposition in downstream regions and
create porosity bands. The coating growth rate differences
between the resulting shadowed and unshadowed regions
cause faster growing deposits to overgrow slower ones,
producing a convergence of porosity bands like what was
observed in the 11 N coatings. In 3SD, the coating
microstructure exhibits no signs of droplets being influ-
enced by drag from the plasma impingement. These
droplets follow a path with a substrate normal component
larger enough to prevent any preferential deposition on
surface asperities or asperity shadowing. Thus, like the
8 M coatings, 3SD microstructures do not contain
columnar structures or porosity bands, and the lamellae
tend to be oriented parallel to the substrate.
The thermal diffusivities of 80 nm powder SPS coatings
were measured in as-sprayed and heat-treated conditions,
and the data were used to calculate coating thermal con-
ductivities. Over the temperature range from 700 to
1200 C, the average thermal conductivities of 2 and 11 N
samples were, respectively, 1.4 and 1.2 W/m/K in the AS
condition and 1.6 and 1.4 W/m/K after 50 h at 1200 C.
The kth increases for these SPS samples were less than
one-third of those for APS YSZ coatings tested under the
same conditions (Ref 10, 32). The decreased change in the
SPS samples kth after heat treatment was attributed to
randomly oriented and isolated interlamellar pores,
implying the 2 and 11 N coatings had void structure
characteristics similar to an EB-PVD coating.
Acknowledgments
Major portions of this research were funded by the
National Science Foundation via grant CMMI-0456534.
Ames Laboratory is operated for the U.S. Department of
Energy by Iowa State University under Contract No. DE-
AC02-07CH11358. Use of the Advanced Photon Source at
Argonne National Laboratory was supported by the U.S.
Department of Energy, Office of Science, Office of Basic
Energy Sciences, under Contract No. DE-AC02-
06CH11357. This project involved research sponsored by
the Assistant Secretary for Energy Efficiency and
Renewable Energy, Office of FreedomCAR and Vehicle
Technologies, as part of the High Temperature Materials
Journal of Thermal Spray Technology
Laboratory User Program, Oak Ridge National Labora-
Peer Reviewed
tory, managed by UT-Battelle, LLC, for the U.S.
Department of Energy under contract number DE-AC05-
00OR22725.
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Journal of Thermal Spray Technology